Treatment of hydrocarbon oils



Q55 effect upon the equipment, e. g., acetic acid,

Patented Dec. 5, 1933 4 UNITED "STA res TREATMENT OF HYDROCARBON OILS Gustav Eglorf, Chicago, 111., assi to Universal Oil Products Company, Chicago,;lll., a corporation of South Dakota Application February 1930 Serial No. 427,954

1 No Drawing.

2 claims; (01. 196- 53)- This invention relates to a process for the,

treatment ofhydrocarbon oils, and refers more particularlyto a process forthe hydrogenation of oils at elevated temperatures.

Among the objects of the process is to increase the yield of the lower boiling productsmade by the thermal? decompositions or cracking of higher boiling oils; to saturate in part the more highly unsaturated hydrocarbons, especially those whichform gums, polymers, and other undesirable materials in the motor fuel product; and to desulfurize in part the hydrocarbons to render them more suitable for motor fuel and to facilitate and reduce the cost of refining.

It is not the purpose of this invention necessarily to completely saturate the hydrocarbons of the olefin series to produce parafiin hydrocarbons, but rather to add hydrogen in regulated amounts to the more highly unsaturated hydrocarbons for the aforementioned purposes.

Gasoline, which is the major product ofthe cracking process, contains highly unsaturated hydrocarbons which upon standing polymerize and oxidize to form gums, tars, and other undesirable substances. The presence of sulfur compounds in a motor fuel may result in destructive corrosion of the crankcase and other parts of the motor during combustion and may also result in the destructive corrosion of. the cracking or distillation equipment.

Among the further objects of my invention is the minimizing of these objectionable features. In the specific embodiment of my invention I mix the non-vaporized residue from the reaction chamber of a cracking process, or the residue from the flash chamber of a cracking process, said flashed residue resulting from passing the non-vaporized residue from the reaction chamber into a vessel under reduced pressure, which causes vaporization of a substantial portion of the non-vaporized residue by the self-contained heat within the residue.

In operation the process of the invention, the residue either from the reaction chamber or the flash chamber is heated in the presence of acidic substances and finely divided metals. Any suitable apparatus may be used for this purpose, although I preferably make use of a heating coil, and preferably heating under pressure.

As examples of acids I may use the so-called mineral acids, such as hydrochloric, nitric, and sulfuric, preferably in diluted form, or a large number of organic acids which I preferably use because of their less corrosive or destructive propionic acid, naphthenic acid, et cetera. I may also use substances which are more or less acidic in nature such as phenols; the naphthenic acids and phenols may be derived from petro leum or its products, which makes the use oi 60. these materialseconomically sound. The organic acids such as acetic and propionic acids and acidic materials such as naphthenic acids and phenols/are soluble in hydrocarbon oils, which gives a good distribution of the reacting materials and promotes the desired reaction. The salts formed from the reaction between the metals and acidic substances may exert a catalytic effect upon the reactions.

As examples of metals I may use sodium, 130- tassium, calcium, magnesium, zinc, aluminum, iron, tin, and others, including alloys and amalgams, preferably metals which are electro-negative to hydrogen, 1. e., above hydrogen in the electromotive series, and which will liberate hydrogen from acidic substances.

The acid substances react with the finely divided metals forming hydrogen in situ. The newly liberated hydrogen which is more active than ordinary molecular hydrogen and is sometimes spoken of as being in the nascent state, reacts with the chemically unsaturated portions of the oil as well as with sulfur compounds, saturating in part the olefinic hydrocarbons and reducing some of the sulfur compounds to hydrogen sulfide which may readily be removed from the final products.

As examples of metals, I may use sodium, potassium, calcium, magnesium, zinc, aluminum,

iron, tin, and others, including alloys and amalgams preferably the metals which are electropositive to hydrogen and which liberate hydrogen from steam. The corresponding oxides of the metals formed by the reaction with steam have some catalytic action in promoting the hydrogenation and desulfurization reaction as well as assisting in the cracking reaction. The

use of finely divided metals has an additional advantage in that the finerthe metal the greater the surface exposure and consequently the greater the velocity or rate of reaction.

In addition to the above I may also add molecular hydrogen to the materials undergoing reaction in order to assist in the reaction, or I may add gasses containing hydrogen such as gases from oil cracking, coke oven gas, producer gas, natural gas, et cetera.

In operating the process of the invention I may make use of any conventional apparatus or equipment suitable for cracking, but preferably I make use of a cracking system consisting of heating tubes or elongated pipe or heating coil in combination with a reaction chamber, dephlegmator or fractionating means and the auxiliary cooling, condensing, and collecting devices. In the operation of theprocess I preferably return the reflux or distillates condensed in the dephlegmating or fractionating means to the heating element for reconversion.

Preferably, the oil is heated to a cracking temperature, although my invention contemplates operating the process at lower temperatures also. Preferably, the process is operated at atmospheric pressure or at superatmospheric pressure, and may in some cases also be operated at atmospheric or reduced or sub-atmospheric pressures. Generally I make use of superatmospheric pressures ranging from pounds to 3000 pounds, more or less, and at temperatures of from approximately 400 to 1400 As an example of the results obtained by the process, a 27 degree Baum gravity Mid-Continent topped crude When subjected to a cracking temperature of approximately 920 F. and a pressure of approximately 1,000 pounds, shows an approximate yield of gasoline of sixty percent, in addition to approximately fifteen percent of pressure-distillate bottoms or gas oil which may be utilized as recycle stock and a liquid residue amounting to approximately 35 percent of the raw charge and containing less than two percnt of sludge and suspended coke. Approximately five percent coke and gas are also formed. The sulfur content of the gasoline produced, which would normally be approximately 0.3 percent., may be reduced to approximately 0.1 percent.

The above example is illustrative and should not be considered as a limitation upon the broad spirit and scope of the invention.

I claim as my invention:

1. A process for treating residuum resulting from the pressure cracking of hydrocarbon oils which comprises removing such residuum from the cracking process and adding thereto, While still in heated condition, an oil soluble acidic material and a metal capable of reacting with each other to form hydrogen, and subjecting the re- GUSTAV EGLOFF.

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